EP1366104B1 - Bioabbaubare polymere, verfahren zu deren herstellung und verwendung als schmelzklebstoff - Google Patents

Bioabbaubare polymere, verfahren zu deren herstellung und verwendung als schmelzklebstoff Download PDF

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Publication number
EP1366104B1
EP1366104B1 EP02702961A EP02702961A EP1366104B1 EP 1366104 B1 EP1366104 B1 EP 1366104B1 EP 02702961 A EP02702961 A EP 02702961A EP 02702961 A EP02702961 A EP 02702961A EP 1366104 B1 EP1366104 B1 EP 1366104B1
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Prior art keywords
mol
lactic acid
acid
hot melt
molecular weight
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French (fr)
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EP1366104A2 (de
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David Neal Lewis
Gerrit Schutte
Henk Westerhof
Jane Janssen
William E. Kelly
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Tate and Lyle PLC
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Tate and Lyle PLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable
    • Y10T428/2817—Heat sealable
    • Y10T428/2826—Synthetic resin or polymer

Definitions

  • the invention is directed to methods for preparing environmentally degradable polymeric compounds as well as to their use.
  • Hot melt adhesives and coatings are used for a wide variety of commercial applications.
  • the primary advantage of hot melt adhesive and coating systems is these systems require no carrier fluid or solvent for application to a substrate and, as a consequence, the need for subsequent evaporation of solvent or carrier fluid is eliminated.
  • the lack of a drying or evaporation step allows these hot melt adhesive and coating systems to eliminate the hazards associated with use of solvents and the environmental impact of volatile organic compounds (VOC).
  • Hot melt adhesive formulations can be varied over a wide range of adhesive properties from pressure sensitive to non-pressure sensitive in character. Pressure sensitive adhesives are used in applications where room temperature tack and long open times are required. Examples of such applications are adhesive tapes, disposable products like diapers, sanitary and incontinence pads.
  • Non-pressure sensitive hot melts are used in applications like carton sealing, paper bag end sealing, telephone book and catalogue book-binding.
  • Hot melt coating applications would include food trays, deli trays, disposable paper carton containers or other containers where a gross barrier would be needed.
  • Hot melt adhesives and coatings have typically been based on petroleum based polymers.
  • Thermoplastic elastomers are used as the polymer component in the hot melt adhesives, which generally fall into three types: 1. petroleum based polymers such as polyethylene, polypropylene, ethylene-vinyl acetate, styrene block copolymers (e.g. styrene isoprene styrene, styrene butadiene styrene); 2. polyurethanes; and 3. polyester/polycarbonate materials.
  • petroleum based polymers such as polyethylene, polypropylene, ethylene-vinyl acetate, styrene block copolymers (e.g. styrene isoprene styrene, styrene butadiene styrene); 2. polyurethanes; and 3. polyester/polycarbonate materials.
  • thermoplastic elastomers have certain drawbacks in their properties and manufacturing.
  • the styrenic block copolymers are usually made by ionic polymerization that require the exclusion of oxygen and moisture of the system. The viscosity is high and the softening point is low.
  • the polyurethanes are not thermally stable. Polyester must be synthesized under high temperature and vacuum. Moreover, they are very resistant to degradation.
  • biodegradable hot melt adhesives were developed. Usually, hot melt adhesives are fomulations containing base resins combined with plasticizers, tackifiers and other additives in order to reach diversified adhesive properties. In typical hot melt formulations, tackifier agents, plasticizers, and extenders like waxes are used to vary adhesion and flow characteristics. These products have the disadvantage of poor environmental degradability.
  • environmentally degradable refers to products which are compostable and/or biodegradable, as is reflected by a substantial loss of mechanical properties (tensile strength, elongation to break, toughness) or structural integrity (breaks into small pieces) upon contact with moisture at ambient or elevated temperature conditions (for example, in a composting operation) during a prolonged period, i.e. typically more than one month.
  • mechanical properties tensile strength, elongation to break, toughness
  • structural integrity breaks into small pieces
  • Blends of polylactides and polycaprolactones for film applications are known from DE 4300420 .
  • This publication describes the reaction of polylactide and polycaprolactone via a ring opening reaction.
  • EP A 0765913 describes a copolymer of high molecular weight polycondensated polylactic acid polymer with C4-C20 aliphatic carboxylic acid polymer.
  • the polymers are used to prepare packaging products via moulding, film extrusion, fibre extrusion and the like.
  • the blocks have a long length, resulting in polymers with a high mechanical strength .
  • the process to prepare these polymers requires the removal of residual monomer.
  • US 5,646,217 describes the transesterification of poly (hydroxyalkonates) with polycaprolactone or polylactide using titanium n-butoxide and antimony oxide.
  • the used building blocks are long chain components having a molecular weight of more than 50,000 g/mol and are used for a very high molecular weight blend.
  • the polymers may be used for applications like films, moldings and shaped articles.
  • EP 0992529 A2 describes melt blending and controlled transesterification to modify blocks of ring opened polyglycolide, polyglycolide-lactide copolymers to make filaments for suture applications with a controlled block copolymer structure.
  • Another object of the invention is to provide a novel method to prepare an environmentally degradable material suitable as a hot melt base resin.
  • Patent publications WO-A-94/10257 , US-A-5 252 646 , and US-A-5 312 850 disclose compositions comprising 20 wt.% to 98 wt.% of a polylactide (PLA) homo- or copolymer containing at least 20 molar percent of the lactide component; 2 to 80 wt.% of a polar tackifier having a Ring and Ball softening point (as described by ASTM E-26) greater than 60°C; 0 to 50 wt.% of a plasticizer; 0 to 30 wt.% of a wax diluent; 0 to 3 wt.% of a stabilizer; and 0-20 wt.% of a polymer.
  • PLA polylactide
  • the last component could be certain hydrophilic polymers such as starch, polyvinyl alcohol, hydroxyethyl cellulose, polyvinyl methyl ether, poly (ethylene oxide), or poly (hydroxybutyrate/hydroxyvalerate), which will function to increase the water sensitivity of the adhesives.
  • it could also be a kind of thermoplastic polymer such as ethylene vinyl acetate, ethylene acrylic acid, ethylene methyl acrylate and ethylene n-butyl acrylate copolymers as well as caprolactone polymers to import flexibility, toughness and strength.
  • These methods use polylactides or polylactic acid polymers synthesized from lactide. Lactide is a cyclic diester obtained from the intermolecular coupling of two lactic acid molecules. The process for producing and purifying lactide and subsequent polymerization of lactide to make a polylactide is expensive and often cumbersome.
  • the present inventors found that when pure lactic acid polycondensates reach a Mw of 3000-5000 g/mol they tend to stiffen.
  • the term "molecular weight” as used herein refers to the weight average molecular weight (Mw) as measured for instance by gel permeation chromatography (GPC). Oligomers having a Mw higher than 3000-5000 g/mol may become very brittle. This is attributed to a glass transition temperature (Tg) that is too high.
  • Tg glass transition temperature
  • the present inventors found that a lactic acid polycondensate starts to lose its surface tackiness at room temperature if polycondensate molecules reach a Mw above 3000 g/mol. The tackiness is totally gone at values of Mw above 10000 g/mol.
  • These higher Mw polycondensates need to be in a molten state to display adhesion and to make them stick to metals, polymers, and paper.
  • a compound should provide for an improvement in at least some of the other aspects that are important in environmentally degradable hot melt resins. These aspects include: open time (defined as the time in which the hot melt still retains its adhesive character. After this time, no substantial adhesion occurs), Tg (which should be decreased), and UV curability, when applicable.
  • the compounds should be relatively easy to manufacture at a lower cost than prior art methods.
  • the present invention relates to a method as defined in claim 1.
  • hot melt type applications are hot melt base resins, hot melt coatings and hot melt adhesives.
  • a method according to the invention is used to prepare an environmentally degradable polymeric compound, suitable for use as a hot melt base resin or for a hot melt type application, which compound comprises 50 to 99 wt.% polylactic acid comprising chains, each of said chains having a Mw of from 500 to 50 000 g/mol, to which chains a flexibilizing aliphatic polyester having a Mw of from 200 to 50 000 g/mol, is coupled, wherein the amount of aliphatic polyester in the compound is 1 to 50 wt.%.
  • the molecular weight as used herein is defined as the weight average molecular weight (Mw) as determined by GPC using polystyrene as a standard.
  • a preferred polymer compound according to the invention has a distinct branched structure.For instance, in a more specific example, it has been found that if dimethylol propionic acid (which contains two hydroxyls and one carboxylic acid group) is used in a polycondensation reaction with lactic acid, the resulting polymer will be a three arm star polymer with one carboxylic acid terminal group and two hydroxyl terminal groups, provided the polymerization is not carried to the gelation point.
  • polyester species act as flexibilizing linkers or couplers between polycondensated lactic acid groups. This solves the problem of the brittleness, which is associated with pure lactic acid oligomers.
  • the compound prepared by the method of the invention may, for example, be in the shape of a star having a core of polyester moiety at the core, while the arms are formed by the lactic acid oligomers.
  • the compound prepared may be in the form of a partial network containing polyester stars connected by lactic acid chains.
  • the molecular weight, Mw, of the aliphatic polyester is according to the present invention from 200 to 50 000 g/mol. Values above 50 000 g/mol are generally too viscous to be mixed properly and, as a result, can usually not provide sufficient coupling sites. Polyesters having molecular weights below 200 g/mol are generally too small to provide adequate flexibility to the final compound.
  • the Mw of the aliphatic polyester is from 1 000 to 40 000 g/mol. Very good results have been achieved with an aliphatic polyester having an Mw from 1000 to 10 000 g/mol.
  • the softening temperature of an environmentally degradable polymer compound according to the invention is usually less than 120 °C(as measured with by ASTM E28: Ring and Ball Method). Very good results have been obtained with a copolymer compound having a softening temperature of less than 105 °C.
  • the glass transition temperature (Tg) of a polymer compound according to the invention is preferably 25 °C or less.
  • the glass transition temperature is defined herein as the glass transition temperature as measured by differential scanning calometry as outlined in ASTM method D3418 (Standard Test Method for Transition Temperatures of Polymers by Thermal Analysis).
  • the melt viscosity of a copolymer compound prepared according to the invention is preferably in the range of 0.1 Pa.s to 400 Pa.s at a measuring temperature of 160 °C at a shear rate between 100 and 2000 s -1 , e.g. over a shear rate range of 250-800 s -1 . More preferred the viscosity is in the range of 0.1 Pa-s to 400 Pa-s between 100°C and 180°C at a shear rate between 100 and 2000 s -1 , e.g. over a shear rate range of 250-800 s -1 .
  • the melt viscosity is used herein is defined as the value as measured using a cone and plate rheometer like the ThermoHaake RS300.
  • the extensional melt strength of a polymer compound prepared according to the invention is preferably less than 0.5 cN (as measured on a Gottfert Rheotens Model 71.97 as described in the paper by H.M. Laun et al, "A recursive Model for Rheotens Tests", Journal of Rheology, Volume 41(3) 1997 and in A. Gottfert et al, Polym. Eng. Sci. 36(7), pp. 925-935 (1996) ).
  • a polymer compound with such a low melt strength and/or melt viscosity has shown to be very uniformly spreadable when used.
  • the polylactic acid comprising groups may according to the present invention contain fragments derived from other monomers as well.
  • the chains may contain other polycondensable combinations of L-lactic acid with D-lactic acid or with D,L-lactic acid or any other hydroxycarboxylic acid, such as glycolic, hydroxycaproic, hydroxyl valeric, etc , or combinations with diols, polyols (triols, tetrols, hexols, etc .) polymer diols, diacids, di, tri or tetra anhydrides or polyanhydrides, or aliphatic polyesters, etc.
  • the majority of these groups i.e .
  • the polylactic acid comprising groups are derived from lactic acid. Most preferably, however, these groups consist essentially of polylactic acid.
  • the Mw of the polylactic acid comprising groups is from 500 to 50 000 g/mol. Again, values above 50 000 g/mol are generally too viscous to be mixed properly and, as a result, can usually not provide sufficient coupling sites. Polylactic acid chains having Mw values below 500 g/mol will result in a system requiring an extensive polycondensation time to reach acceptable properties.
  • the Mw of the polylactic acid comprising groups is from 1500 to 40 000 g/mol, more preferably 1500 to 10 000 g/mol.
  • the polylactic acid comprising groups should be present in the compounds prepared according to the invention in an amount of from 50 to 99 wt.%.
  • the aliphatic polyesters are polycaprolactone polyols (diols, triols, tetrol or higher).
  • Preferred compounds for use as the flexibilizing aliphatic polyester are polycaprolactone diol, polycaprolactone triol and polycaprolactone tetrol.
  • Hot melt base resins prepared according to the current invention may be produced by controlled polycondensation of L-lactic acid, D-lactic acid or D,L lactic acid (also known as 2-hydroxypropanoic acid) in the presence or absence of a catalyst followed by a condensation coupling reaction with the aliphatic polyester to produce hot melt base resins with the desired flowability or viscosity, flexibility, pot life, open or setting time, tensile strength and extensibility.
  • the hot melt base resins prepared according to the present invention may also include any polycondensable combinations of L-lactic acid with D-lactic acid or with D,L-lactic acid or any other hydroxycarboxylic acid (glycolic, hydroxycaproic, hydroxylvaleric, etc) or combinations with diols, polyols (triols, tetrols, hexols, etc) polymer diols, diacids, di, tri or tetra anhydrides or polyanhydrides, or aliphatic polyesters.
  • the polycondensed polymer prepared according to the present invention may be prepared without catalyst in the presence of heat and sufficient vacuum or in the presence of catalysts which promote esterification or transesterification. This type of reaction is carried out relatively more simply than ring-opening polymerization.
  • Suitable catalysts for this purpose are conventional transesterification catalysts, which comprise tin(II), tin(IV), iron(II), iron(III), zinc, calcium and/or magnesium metals; for example stannous oxide, stannous chloride, stannous bis 2-ethyl hexanoate (also known as stannous octoate), stannous acetate, stannous acetylacetonate, stannous lactate and zinc salts like zinc stearate, zinc oxide, zinc chloride, zinc lactate, iron (III) salts like ferric acetate and ferric lactate, etc.
  • Preferred catalysts are stannous oxide and stannous chloride.
  • Other suitable catalysts for this purpose are transition metal catalysts: e.g.
  • rare earth catalysts e.g., aluminum, iridium, titanium, nickel, chromium, vanadium, hafnium, manganese, tungsten, tantalum, platinum, palladium, samarium, gallium, germanium, indium, cobalt, rhodium, rhenium, ruthenium, thallium, bismuth, cadmium, thorium and/or zirconium comprising compounds, which may be used in combination with the above-mentioned conventional transesterification catalysts.
  • rare earth catalysts e.g.
  • yttrium europium, yttrium, erbium, dysprosium, holmium, neodymium, gadolinium, lutetium, lanthanum, praseodymium, terbium., thulium and/or ytterbium comprising compounds, which may also be used in combination with the above-mentioned conventional transesterification catalysts or transition metal catalysts.
  • the above-mentioned catalysts may also be used in combination with acidic catalysts, such as sulfuric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, toluene sulfonic acid.
  • acidic catalysts such as sulfuric acid, phosphoric acid, hydrochloric acid, methanesulfonic acid, toluene sulfonic acid.
  • the preparation may be carried out using conventional polymerization and polycondensation techniques.
  • the synthesis may be carried out using a two step route, in which in Step 1 the polylactic acid comprising groups are synthesized by polymerization.
  • a catalyst may be used to decrease the reaction time.
  • a low Mw acid or alcohol may be used as an initiator for the polycondensation, in which case a carboxylic or hydroxyl functional product is formed, rather than a bi-functional product.
  • Other hydroxyacids than lactic acid can be used for copolymerisation as well.
  • a lactic acid based copolymer is obtained, having a Mw in the range of 500 to 50 000 g/mol.
  • Suitable reaction conditions for this first step comprise a temperature of from 150 to 260°C preferably from 180 to 200 °C, and a reaction time of 1 h to more than 20 h.
  • the synthesis is preferably carried out in a vacuum, preferably at less than 15 mbar, dependent upon the amount of water present in the reaction mixture. Most preferred are pressures of 0 to 15 mbar.
  • Step 2 comprises the coupling of the polycondensated lactic acid oligomer made in step 1 with one or more "flexible" aliphatic polyester components by esterification and/or transesterification or via chain coupling with a chain coupling agent.
  • Low Mw components may also be used to change the hydroxyl/carboxyl (OH/COOH) ratio in order to attain a desired molecular weight or a desired functionality.
  • Multifunctional components may also be used to obtain a specific functionality. In this way a flexible copolymer with a molecular weight of 500 to 100 0000 g/mol may be obtained.
  • a polymer with a molecular weight of 500 to 80 000 g/mol has been found to have particularly good properties for a hot-melt application.
  • Suitable reaction conditions for Step 2 comprise a reaction temperature of 160 to 270°C, preferably of from 190 to 220°C, a reaction time from 0.2 to 10 h, while the reaction is preferably carried out in a vacuum, preferably at below 50 mbar, most preferably at from 10 to 20 mbar.
  • a rotary evaporator or another standard polycondensation setup may be used to carry out both steps.
  • the preparation may also be carried out in a single step, viz . by combining Steps 1 and 2.
  • the components mentioned above for Steps 1 and 2 are mixed.
  • the reaction is carried out at a temperature of 160 to 270°C, preferably 190 to 220 °C, during 1 to more than 20 hours at a vacuum pressure of down to less than 15 mbar, depending on the amount of water present in the reaction-mixture, preferably 0 to 1 mbar.
  • Mw Mw weight
  • the Mw of the polymeric compound of the invention is preferably from 700-100 000 g/mol, more preferably from 700-80 000 g/mol, even more preferably from 2000 to 50 000 g/mol.
  • Step 1 and 2 as described above, are followed by a Step 3, which comprises endcapping or chain extending of the polymers chain to improve the stability of the polymer, increase the molecular weight or to create different functionality or non-functionality.
  • L-Lactic acid, D-Lactic acid and DL Lactic acid may be used to prepare the polylactic acid comprising groups.
  • Suitable polycondensation catalysts are the conventional catalyst used for this purpose, such as tin oxide, tin chloride, zinc stearate, toluene sulfonic acid (TSA), etc.
  • the aliphatic polyester which is used as a "flexible component” may be a polycaprolactone polyol (diol, triol or tetrol) with a Mw of 100 to 50 000 g/mol, preferably of 200 to 40 000 g/mol.
  • the low molecular weight alcohols mentioned above may be selected from diols such as ethyleneglycol, propyleneglycol, butanediol, hexanediol, neopentylglycol, 1,4 dimethylolcyclohexane, 2,2,4-trimethylpentanediol-1,3, 1,3-butenediol, etc.; triols such as trimethylolpropane, trimethylolethane, etc.; and polyols such as pentaerythritol, dipentaerythritol, etc .
  • the low molecular weight acids may be selected from dicarboxylic acids such as adipic acid, sebatic acid, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid; phthalic anhydride, isophthalic anhydride, etc .; and polycarboxylic acids such as trimellitic anhydride, pyromellitic dianhydride, etc .
  • hydroxyacids such as dimethylolpropionic acid, etc .
  • lactones such as butyrolactone, ⁇ -caprolactone, etc .
  • aminoacids aminoalcohols such as taurine
  • hydroxysulfates epoxides such as ethyleneoxide, propyleneoxide, Cardura E, glycidol
  • epoxyacrylics such as glycidylmethacrylate
  • acetic anhydride hydroxyacids such as dimethylolpropionic acid, etc .
  • lactones such as butyrolactone, ⁇ -caprolactone, etc .
  • aminoalcohols such as taurine
  • hydroxysulfates epoxides
  • epoxides such as ethyleneoxide, propyleneoxide, Cardura E, glycidol
  • epoxyacrylics such as glycidylmethacrylate
  • acetic anhydride acetic anhydride
  • Chainextenders or crosslinkers that may used in Step 3, mentioned above, are dianhydrides such as pyromellitic dianhydride; di-or tri-isocyanate such as hexamethylenediisocyanate, isophorone diisocyanate, isocyanurates, allofenates, etc.; diepoxides such as the diglycidylether of butanediol, the diglycidylether of bisphenol A, etc .; diamines such as hexanediamine, polyoxypropylenediamine, etc .; silanes; and peroxides such as benzoylperoxide, T-butyl peroxybenzoate, etc .
  • dianhydrides such as pyromellitic dianhydride
  • di-or tri-isocyanate such as hexamethylenediisocyanate, isophorone diisocyanate, isocyanurates, allofenates, etc.
  • diepoxides such as
  • Polymers produced in the initial polycondensation step have Mw values of between 500 and 50,000 g/mol, preferably 500 to 40 000 g/mol, more preferably in the range of 1500 to 10,000 g/mol.
  • the polylactic acid comprising groups in the coupling step of the current invention can include other degradable aliphatic polyesters, such as polycaprolactones, polyester diols, polyester triols or polyester tetrols or polyester hexols either produced by polycondensation or by ring opening polymerization. These can include copolymers of lactide or glycolide and caprolactone or copolymers comprising other monomers, which may be subjected to ring-opening, such as valerolactone.
  • the preferred coupling polymers are polycaprolactone diols, triols or tetrols, which provide flexibility, extensibility, and a glass transition temperature (Tg) below room temperature (i.e. 25 °C) to the final hot melt base resin.
  • the coupling reaction may include partial transesterification reactions, particularly in the presence of a transesterification catalyst.
  • the Mw of the coupling polymer can be in the range of 200 to 50,000 g/mol, preferably in the range of 200 to 40 000 g/mol and more preferably is in the range of 1000 to 10,000 g/mol.
  • the amount of coupling polymer in the final hot melt base resin varies between 1 to 50 %, preferably in the range of 10 to 30%.
  • the coupling of the polycondensed polymer of the first step and the polymer of the second step can alternatively be accomplished by the use of coupling agents including cyclic anhydrides, mono-, di-, tri- or tetracyclic anhydrides, polyanhydrides, cyclic or glycidal ethers, aliphatic isocynates, aliphatic polyisocyanates, silanes and chlorosilanes.
  • Hot melt base resins of the present invention can be made ultraviolet curable by use of double bond containing diol or diacid components. Properties of the hot melt base resins can be further modified by partial crosslinking with the use of organic peroxides like cumyl peroxide, tertbutyl peroxybenzoate, tertbutyl peroxyacetate, etc .
  • Applications of the environmentally degradable polymeric compounds prepared according to the present invention include hot-melt adhesives and coatings via hot spray, laminates, tie-layers and bonding materials.
  • the polymer obtained has relatively high surface tension, which allows for printing - directly without surface treatment.
  • the resulting material is hot water resistant and not solubilized by hot water.
  • the end use products which may be obtained in accordance with the present invention comprise adhesive materials which are used for carton sealing, booking bindings, adhesive tapes, construction of disposable diapers, sanitary napkins, incontinence pads; and coatings for food trays, deli trays, carton containers or other products where a gross water barrier is desired.
  • the argon is bubbled through the lactic acid solution and the system maintained at 800 mbar vacuum and 180°C temperature until almost the Tin (II) oxide disappears.
  • the liquid will change gradually from dark gray to a hazy clear solution.
  • the vacuum is gradually increased over the next hour to 100 mbar and the argon also subsequently reduced. After this second hour, the argon flow is stopped and the vacuum increased (or pressure reduced) to the maximum amount (5-10 mbar) and the polycondensation reaction continued for 6 hours.
  • the vacuum is released by increasing the flow of argon; increasing the vacuum control setting to atmospheric pressure, then the flask is removed and 96 g (12%) polycaprolactone tetrol (CAPA 205042, obtained from Solvay, having a number average molecular weight (Mn) as determined by end group analysis of 8000 g/mol) is added to the pear shaped flask, after it is removed from the rotary evaporator unit.
  • the vacuum is again set to its maximum value, the oil bath temperature raised to 195°C and the coupling reaction allowed to take place for 4 hours.
  • the final product is a slightly yellow liquid, which upon cooling to room temperature is a slightly flexible solid and has a Mw of 17,400.
  • Calculations in this example are based on the functional groups of the available raw material and will therefore change if different initiation cores are used.
  • Two low Mw caprolactone species from Solvay were used; CAPA 316 (tetra-functional polyol, Mn 1000 g/mol, as determined by end group analysis) and CAPA 205042 (similar to CAPA 316 but with Mn 8000 g/mol).
  • the reaction ratio was based on the functional groups of the caprolactone segment (polyol). Complete reaction between the caprolactone segments and the lactic acid polycondensate segments was assumed. The molecular ratio between the tetra-functional CAPA 205042 (or CAPA 316) and a lactic acid polycondensate segment was 1:4, respectively. One part of a caprolactone segment can react with four parts of a lactic acid polycondensate segment.
  • a desired molecular weight is defined.
  • the amount of lactic acid that is needed can be calculated, since the CAPA segment has a fixed molecular weight.
  • the desired molecular weight of the end product is 28000 g/mol and if CAPA 205042 is used as the flexible segment, which has a Mw of 8000 g/mol, the residual Mw 20000 has to be lactic acid.
  • the amount of raw lactic acid could be calculated, based on the purity and concentration.
  • L-lactic acid was polycondensated until all the free water was removed from lactic acid solution. After removing the water, CAPA 205042 was added to the flask. The esterification reaction was continued in order to obtain polymer with a flexible core, having a Mw of 50 000 g/mol.
  • the desired Mn is 50 000 g/mol.
  • the CAPA segment have a Mn of 8000 g/mol the rest is Lactic acid so 42000 g/mol.
  • the amount of CAPA needed: (647/42000)*8000 123 g.
  • CAPA 205042 122.90 g Reaction Time (min) Temp oil (°C) Press. (mbar) 15 25-110 800 +/- 3 40 110 800 -> 200 40 117 50 110 139 50 130 160 50 100 180 50
  • the polycondensate was opaque, slightly yellow, having little crystallinity.
  • the polycondensate was sticky. Reaction Time (min) Temp oil (°C) Press. (mbar) 60 178 800 ⁇ 70 180 189 70 220 190 200 +Argon flow
  • L-lactic acid 861 g Reaction Time (min) Temp (°C) Press. (mbar) 30 100 800+/-5 150 105 600 15 110 400 75 115 300 40 116 200 70 142 200 235 149-155 200 110 167-173 200 170 176-184 200 270 176-184 200 210 176-184 100 60 176-184 50
  • CAPA 205042 80 g L-lactic acid polycondensate (see above): 200 g Reaction Time (min) Temp (°C) Press. (mbar) 30 133 800 +/- 5 45 144 800 15 154 500 30 156 200 260 175 200
  • the melt was applied to a piece of paperboard fruit tray with a brush.
  • the coated tray did not feel sticky.
  • the fruit tray was filled with water, which was left there for several hours. After removing the water the coating did not show any signs of being dissolved or softened by the water.
  • the material was treated with 0.2 wt% of benzoyl peroxide in order to create entanglements between the molecular chains. Besides crosslinking, peroxides also act as a catalyst deactivator which enhances the stability of the polycondensate.
  • Step 1 polycondensation of L-lactic acid pre-polycondensate with 0.3 wt% SnCl 2 .2H 2 O and 0.3 wt% TSA.
  • L-lactic acid polycon 589 g SnCl 2 ⁇ H 2 O : 1.8 g TSA : 1.8 g
  • Step 2 addition of CAPA 205042.
  • CAPA 205042 110.14 g Reaction Time (min) Temp (°C) Press.
  • (mbar) 70 180 38 +/- 3 20 180 25 110.14 g of CAPA 205042 was added 330 193 20 405 200 20
  • the polycondensate looked brownish.
  • the material was very flexible, non-sticky and found to be water resistant.
  • the material could be used as a flexible coating.
  • the Tin (II) oxide has easily dissolved at 180°C.
  • the liquid will change gradually from a hazy clear solution to a crystal clear solution.
  • the vacuum is gradually increased over the next hour to 100 millibar and the argon also subsequently reduced. After this second hour, the argon flow is stopped and the vacuum increased (or pressure reduced) to the maximum amount (5-10 millibar) and the polycondensation reaction continued for 7 hours. After this time, the vacuum is released by increasing the flow of argon and increasing the vacuum control setting to atmospheric pressure.
  • Aldrich is added to the pear shaped flask after it is removed from the rotary evaporator unit.
  • the vacuum is again set to its maximum value, the oil bath temperature raised to 200°C and the polycondensation reaction allowed to take place for 4 hours.
  • the final product is a slightly yellow liquid, which upon cooling to room temperature is a flexible solid and has a Mw of 12,400, a Tg of -5°C and a Tm of 120°C.
  • the lower molecular weight will have a negative effect on the flexibility.
  • the formulation can be compensated with an extra amount of di, tri or tetra acid (or excess to make the polymer carboxylic functional).
  • the product can be used as a hot melt adhesive. Trying to separate two pieces of cardboard after they are adhered together results in cardboard tear, which means that the adhesive is stronger than the cardboard. By using a slightly higher percentage of caprolactone in the formulation the open time has improved. Even at lower temperatures this adhesive remains its flexibility.
  • the product can also be used as a coating. After hot spraying a flexible non sticky water-resistant coating will be formed. The product is compostable.
  • ThermoHaake RS300 rheometer equipped with a 20 mm 1° angle cone and 20 mm plate test fixture.
  • the test is conducted using a steady shear mode in which the cone rotates at a fixed speed for a given shear rate.
  • the practical limitations of viscosity measurement for polymeric materials are at the lowest shear rate, the noise or uncertainty in the shear stress, which is related to the measured torque.
  • the limitation is when the material begins to experience nonlaminar flow and the beginning of turbulent flow begins. These boundaries are Mw and temperature dependent.
  • the sampling or measuring time varies with the shear rate range covered during a run and the total duration of time.
  • the measuring temperature for the sample was 180°C.
  • the melt viscosity and shear rate were measured at 1 sec. intervals from 0.1 s -1 to 200 s -1 .
  • the molten polylactide exhibits a slightly shear thinning melt viscosity from 1100 Pa-s down to 800 Pa-s over a shear rate range of 2 s-1 to 40 s-1. From 40 s -1 to 90 s -1 , the melt viscosity shows pronounced shear thinning behavior decreasing from 800 Pa-s to 200 Pa-s. Above 90 s -1 , the viscosity is not measurable as the sample experiences nonlaminar flow and does not remain in the test fixture. This point is observable from the flattening and decrease of the shear stress relative to increasing shear rate.
  • a hot melt base resin made using a similar process as outlined in Example 2 was prepared by polycondensating dehydrated L-lactic acid with succinic anhydride and adding tin chloride as catalyst, to make a Mw of 3000 after 8 hrs. Phosphoric acid was then added as a cocatalyst along with an 8000 Mw polycaprolactone tetrol (CAPA 205042) and trimethylol with additional heat and vacuum to couple by condensation and transesterification the aliphatic polyester tetrol, trimethylol and acid ended polycondensated lactic acid polymer together.
  • Phosphoric acid was then added as a cocatalyst along with an 8000 Mw polycaprolactone tetrol (CAPA 205042) and trimethylol with additional heat and vacuum to couple by condensation and transesterification the aliphatic polyester tetrol, trimethylol and acid ended polycondensated lactic acid polymer together.
  • this copolymer material reached an Mw of 45,000 g/mol as measured by GPC using polystyrene standards.
  • This copolymer material was a translucent, slightly yellow and slightly tacky, solid at room temperature. It had a Tg of 18 °C and exhibited no melting point.
  • melt viscosity for this copolymer material was measured at 5 test temperatures: 100°C, 120°C, 140°C 160°C, and 180°C. For comparison with the polylactide described previously, the melt viscosity measurements at 100°C and 180°C are described next.
  • the melt viscosities were measured using the same RS300 rheometer equipped with the same 20 mm cone and plate test fixture used to measure the high Mw polylactide comparative sample. It was found by practice that the measuring shear rate range for these hot melt base resin copolymers was between 100 s -1 and 2000s -1 given the limitations described previously.
  • the melt viscosity was slightly shear thinning across the entire shear rate range of 100 s -1 to 800 s -1 .
  • the melt viscosity decreased from 200 Pa-s at the lowest shear rate to 100 Pa-s at the highest.
  • the material was very slightly shear thinning across the measured shear rate range from 250 s -1 to 2000 s -1 . Over this range, the melt viscosity decreased from 3.9 Pa-s down to 2.9 Pa-s.

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Claims (15)

  1. Verfahren zur Herstellung einer umweltgerecht abbaubaren Polymerverbindung, die zur Verwendung als eine Applikation des Heißschmelztyps geeignet ist, umfassend die folgenden Schritte: Polykondensieren einer Milchsäure zur Bildung eines eine Milchsäure umfassenden Polymers, wobei das Milchsäure umfassende Polymer ein Gewichtsmittel des Molekulargewichts (Mw) im Bereich von 500 bis 50000 g/mol umfasst und mindestens 95 Mol-% sich von Milchsäure herleitende Gruppen umfasst, und Koppeln des eine Milchsäure umfassenden Polymers an einen flexibilisierenden aliphatischen Polyester unter Kondensations- und/oder Transesterifizierungsreaktionsbedingungen, worin der flexibilisierende aliphatische Polyester ein Polycaprolactonpolyol darstellt.
  2. Verfahren nach Anspruch 1, worin die Kondensations- und/oder Transesterifizierungsreaktionsbedingungen das in Kontakt bringen mit einem Katalysator umfassen, welcher Katalysator mindestens ein Metall umfasst, das ausgewählt ist aus: Antimon, Zinn(II), Zinn(IV), Eisen(II), Eisen(III), Zink, Calcium, Magnesium, Übergangsmetallen und Seltenerdmetallen; optional in Kombination mit einem sauren Cokatalysator, der aus Schwefelsäure, Phosphorsäure, Salzsäure, Methansulfonsäure und/oder Toluensulfonsäure ausgewählt ist.
  3. Verfahren nach Anspruch 2, worin der Katalysator Zinn-Oxid, Zinn-Chlorid, Zinn-Lactat, Zinn-2-ethylhexanoat und/oder Zinklactat darstellt.
  4. Verfahren nach einem der vorangehenden Ansprüche, worin das Milchsäure umfassende polykondensierte Polymer und der flexibilisierende aliphatische Polyester durch ein Kopplungsmittel gekoppelt sind.
  5. Verfahren nach einem der vorangehenden Ansprüche, worin das Kopplungsmittel aus der Gruppe ausgewählt ist, bestehend aus cyclischen Anhydriden, bicyclischen Anhydriden, tricyclischen Anhydriden, tetracyclischen Anhydriden, Polyanhydriden, cyclischen Ethern, Glycidylethern, aliphatischen Isocyanaten, aliphatischen Polyisocyanaten, Silanen und Chlorsilanen.
  6. Verfahren nach Anspruch 1, worin eine Polymerverbindung hergestellt wird, welche Verbindung 50 bis 99 Gew.-% Polymilchsäure umfasst, die Ketten umfasst, wobei jede der Ketten ein Gewichtsmittel des Molekulargewichts (Mw) von 500 bis 50000 g/mol aufweist, an welche Ketten ein flexibilisierender aliphatischer Polyester mit einem Molekulargewicht von 200 bis 50000 g/mol gekoppelt ist, worin die Menge des aliphatischen Polyesters in der Verbindung 1 bis 50 Gew.-% beträgt.
  7. Verfahren nach einem der vorangehenden Ansprüche, worin der flexibilisierende aliphatische Polyester ein Molekulargewicht im Bereich von 1000 bis 10000 g/mol aufweist.
  8. Verfahren nach einem der vorangehenden Ansprüche, worin das Molekulargewicht des die Polymilchsäure umfassenden Polymers von 1500 bis 10000 g/mol beträgt.
  9. Verfahren nach einem der vorangehenden Ansprüche, worin die Menge des flexibilisierenden aliphatischen Polyesters von 10 bis 30 Gew.-% beträgt.
  10. Verfahren nach einem der vorangehenden Ansprüche, worin der flexibilisierende aliphatische Polyester aus der Gruppe ausgewählt ist, bestehend aus Polycaprolactondiol, Polycaprolactontriol, Polycaprolactontetrol, Polycarpolactonhexol und Kombinationen davon.
  11. Verfahren nach einem der vorangehenden Ansprüche, worin die Polymilchsäureketten, bevorzugt unter Verwendung eines organischen Peroxids, mindestens teilweise vernetzt sind.
  12. Verfahren nach einem der vorangehenden Ansprüche, worin die umweltgerecht abbaubare Polymerverbindung ein Gesamtmolekulargewicht (Mw) von 700 bis 100000 g/mol, bevorzugt von 2000 bis 50000 g/mol aufweist.
  13. Verfahren nach einem der vorangehenden Ansprüche, worin die umweltgerecht abbaubare Polymerverbindung eine Erweichungs- oder Schmelztemperatur von weniger als 120 °C aufweist.
  14. Verfahren nach einem der vorangehenden Ansprüche, worin die umweltgerecht abbaubare Polymerverbindung eine Schmelzviskosität zwischen 0,1 Pa.s und 400 Pa.s bei einer Scherrate zwischen 100 und 2000 s-1 bei einer Messtemperatur von 160 °C aufweist.
  15. Verwendung einer Verbindung, die mittels des Verfahrens nach einem der Ansprüche 1 bis 14 als ein Heißschmelzklebstoff; eine Heißschmelzbeschichtung, wie zum Beispiel eine sprühbare Heißschmelzbeschichtung oder eine applizierte Heißschmelzbeschichtung, erhalten wird.
EP02702961A 2001-03-02 2002-03-04 Bioabbaubare polymere, verfahren zu deren herstellung und verwendung als schmelzklebstoff Expired - Lifetime EP1366104B1 (de)

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PCT/NL2002/000137 WO2002070583A2 (en) 2001-03-02 2002-03-04 Environmentally degradable polymeric compounds, their preparation and use as hot melt adhesive
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Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI115217B (fi) * 2001-10-15 2005-03-31 Jvs Polymers Oy Biohajoava pinnoite
ATE518932T1 (de) * 2003-02-21 2011-08-15 Metabolix Inc Pha-mischungen
US8283435B2 (en) 2003-02-21 2012-10-09 Metabolix, Inc. PHA adhesive compositions
EP1704180B1 (de) 2003-12-30 2008-09-10 Metabolix, Inc. Nukleierungsmittel
US7393590B2 (en) * 2004-02-27 2008-07-01 Cereplast, Inc. Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising Biodegradable poly(lactic acid) polymer compositions
TW200628296A (en) * 2004-11-19 2006-08-16 Mitsubishi Plastics Inc Light reflecting body and manufacturing method of light reflecting body
US7666946B2 (en) 2006-01-27 2010-02-23 Arkema Inc. Blends of biopolymers with acrylic copolymers
MX2009000525A (es) 2006-07-14 2009-01-27 Kimberly Clark Co Poliester alifatico biodegradable para usarse en telas no tejidas.
MX2009000527A (es) 2006-07-14 2009-01-27 Kimberly Clark Co Acido polilactico biodegradable para su uso en telas no tejidas.
US8710172B2 (en) 2006-07-14 2014-04-29 Kimberly-Clark Worldwide, Inc. Biodegradable aliphatic-aromatic copolyester for use in nonwoven webs
WO2008054387A1 (en) 2006-10-31 2008-05-08 Societe De Technologie Michelin Method for improved retread endurance
US8870871B2 (en) * 2007-01-17 2014-10-28 University Of Massachusetts Lowell Biodegradable bone plates and bonding systems
AU2007358034B2 (en) 2007-08-22 2014-01-23 Kimberly-Clark Worldwide, Inc. Multicomponent biodegradable filaments and nonwoven webs formed therefrom
FR2921547A1 (fr) * 2007-09-28 2009-04-03 Acting Sarl Pinceau
WO2009045564A1 (en) * 2007-10-01 2009-04-09 Arkema Inc. Blends of biodegradable polymers and acrylic copolymers
BRPI0822434B1 (pt) 2008-05-30 2018-05-29 Kimberly-Clark Worldwide, Inc. Trama não tecida, artigo absorvente e método para formar a trama não tecida
KR100962387B1 (ko) * 2008-06-05 2010-06-10 제일모직주식회사 폴리유산 수지 조성물
FR2934272B1 (fr) * 2008-07-24 2013-08-16 Roquette Freres Procede de preparation de compositions a base de matiere amylacee et de polymere synthetique.
FR2937975B1 (fr) * 2008-11-06 2011-05-13 Cvlc Adhesif thermofusible a faible temperature d'application a base de polymere d'acide lactique et procede de preparation
US8016980B2 (en) 2008-11-25 2011-09-13 Dixie Consumer Products Llc Paper products
TWI377226B (en) * 2008-12-31 2012-11-21 Far Eastern New Century Corp Poly (lactic acid) resin composition for preparing transparent and impact-resistant article, article prepared therefrom and preparation process thereof
CN102648234A (zh) * 2009-12-08 2012-08-22 国际纸业公司 由生物基材料的反应性挤出产物制得的热成型制品
FI124269B (fi) 2010-03-12 2014-05-30 Stora Enso Oyj Kuumasaumautuva biohajoava pakkausmateriaali, sen valmistusmenetelmä ja siitä muodostettu tuotepakkaus
US8461262B2 (en) 2010-12-07 2013-06-11 Kimberly-Clark Worldwide, Inc. Polylactic acid fibers
US9969149B2 (en) * 2011-06-23 2018-05-15 Agc Glass Europe Polymer material based on polylactic acid
US9475930B2 (en) 2012-08-17 2016-10-25 Metabolix, Inc. Biobased rubber modifiers for polymer blends
WO2014074115A1 (en) * 2012-11-09 2014-05-15 Danimer Scientific, Llc Hot melt adhesives
DE102013004909A1 (de) 2013-03-22 2014-10-09 Jowat Ag Neue Klebstoffzusammensetzungen auf Basis nachwachsender Rohstoffe und deren Verwendung
DE102013205144A1 (de) 2013-03-22 2014-09-25 Novamelt GmbH Klebstofftechnologie Klebstoffzusammensetzung auf Basis von gegebenenfalls modifiziertem Polylactid, Verfahren zu deren Herstellung sowie Verwendung der Klebstoffzusammensetzung
DE102013205110A1 (de) * 2013-03-22 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Klebstoffzusammensetzung auf Basis eines Polyesterurethans und Polyesterurethan
EP3004225A1 (de) 2013-05-30 2016-04-13 Metabolix, Inc. Rezyklatmischungen
EP2832762A1 (de) * 2013-07-30 2015-02-04 Sulzer Chemtech AG Verfahren zur Herstellung von Poly(2-Hydroxyalkansäure), und dadurch erhaltbare Poly(2-Hydroxyalkansäure)
CN106459544B (zh) 2014-03-27 2021-10-01 Cj 第一制糖株式会社 高度填充的聚合物体系
ES2765700T3 (es) * 2015-10-01 2020-06-10 Purac Biochem Bv Adhesivo termofusible no reactivo con mejorador de tiempo de fraguado
AU2016355420B2 (en) * 2015-11-19 2019-11-14 Danimer Bioplastics, Inc. Polymer compositions and hot-melt adhesives formed therefrom
EP3214106B1 (de) * 2016-03-03 2019-01-23 PURAC Biochem BV Nichtreaktiver schmelzklebstoff mit lactidbasiertem copolymer
SG11201906606WA (en) * 2017-01-20 2019-08-27 Danimer Bioplastics Inc Biodegradable hot melt adhesives
CN107903599A (zh) * 2017-12-14 2018-04-13 陈逊 一种聚乙醇酸树脂挤出复合材料及其制造方法
WO2020051422A1 (en) 2018-09-07 2020-03-12 Bostik, Inc. Compostable hot melt adhesive

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4057537A (en) * 1975-01-28 1977-11-08 Gulf Oil Corporation Copolymers of L-(-)-lactide and epsilon caprolactone
US5028667A (en) * 1989-09-29 1991-07-02 E.I. Du Pont De Nemours And Company Yttrium and rare earth compounds catalyzed lactone polymerization
US5169889A (en) * 1992-01-27 1992-12-08 National Starch And Chemical Investment Holding Corporation Poly hydroxybutyrate/hydroxyvalerate based hot melt adhesive
US5312850A (en) * 1993-01-04 1994-05-17 National Starch And Chemical Investment Holding Corporation Polylactide and starch containing hot melt adhesive
US5252646A (en) * 1992-10-29 1993-10-12 National Starch And Chemical Investment Holding Corporation Polylactide containing hot melt adhesive
AU659353B2 (en) 1992-10-29 1995-05-11 National Starch And Chemical Investment Holding Corporation Polylactide containing hot melt adhesive
NL9201949A (nl) 1992-11-06 1994-06-01 Univ Groningen Met rubber gemodificeerde polylactide-samenstelling.
GB9223351D0 (en) * 1992-11-06 1992-12-23 Ici Plc Polyesters
DE4300420A1 (de) * 1993-01-09 1994-07-14 Basf Ag Polylactide mit erhöhter Flexibilität
EP0723572B1 (de) * 1993-10-15 1999-12-08 H.B. Fuller Licensing & Financing, Inc. Biologisch abbaubare bzw. kompostierbare hot melt-klebstoffe, enthaltend polyester auf basis von milchsäure
US5399666A (en) * 1994-04-21 1995-03-21 E. I. Du Pont De Nemours And Company Easily degradable star-block copolymers
US5616657A (en) * 1994-07-20 1997-04-01 Dainippon Ink And Chemicals, Inc. Process for the preparation of high molecular lactic copolymer polyester
EP0699800A2 (de) * 1994-08-31 1996-03-06 National Starch and Chemical Investment Holding Corporation Heissschmelzbare Beschichtungen für Papier und Pappe
US5574076A (en) 1995-05-03 1996-11-12 National Starch And Chemical Investment Holding Corporation Sucrose benzoate as a tackifier for water sensitive or biodegradable hot melt adhesives
US5583187A (en) * 1995-05-03 1996-12-10 National Starch And Chemical Investment Holding Corporation Hot melt adhesives based on hydroxy-functional polyesters
US5747637A (en) * 1995-09-07 1998-05-05 Mitsui Toatsu Chemicals, Inc. Bioabsorbable polymer and process for preparing the same
US5686540A (en) * 1995-09-29 1997-11-11 Dainippon Ink And Chemicals, Inc. Process for the preparation of lactic acid-based polyester
US5719256A (en) * 1995-10-19 1998-02-17 Mitsu Toatsu Chemicals, Inc. Process for preparing polycondensation polymer compound
US5756651A (en) * 1996-07-17 1998-05-26 Chronopol, Inc. Impact modified polylactide
US6287499B1 (en) * 1998-10-09 2001-09-11 United States Surgical Corporation Process of making bioabsorbable block copolymer filaments
DE60137933D1 (de) * 2000-07-17 2009-04-23 Mitsui Chemicals Inc Auf milchsäure basierende harzzusammensetzungen und daraus hergestellte formteile
KR100453130B1 (ko) * 2001-11-21 2004-10-15 한국과학기술연구원 구조적 배열이 일정한 생분해성 락타이드(글리콜라이드또는 락타이드/글리콜라이드)/ε-카프로락톤 멀티블록공중합체 및 이의 제조 방법

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WO2002070583A2 (en) 2002-09-12
US7868101B2 (en) 2011-01-11
DE60224505D1 (de) 2008-02-21
PT1366104E (pt) 2008-04-18
AU2002236346A1 (en) 2002-09-19
US20070243374A1 (en) 2007-10-18
DK1366104T3 (da) 2008-05-26
US7465770B2 (en) 2008-12-16
WO2002070583A8 (en) 2003-11-13
US20040143072A1 (en) 2004-07-22
ATE383386T1 (de) 2008-01-15
WO2002070583A3 (en) 2002-11-28

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